Method for manufacturing sulphur colors



Patented Nov. 8, 1938 UNITED," STATES 1 2,136,017 METHOD ron MANUFACTURING SULPHUR COLORS Simon Norman, Providence, R. 1., assignor to' Industrial Dyestuff Company, East Providence, R. I., a corporation of Rhode Island I No Drawing.

" Application June 22, 193

Serial No. 86,699

. 8 Claims.

This case in a continuation in part of my earlier application, Serial No.. 46, 9, filed October24, 1935.

:This invention relates to an improved manu:- facture of sulphur colors by a new method, whichf can be used on a large variety of intermediates that can be thionated.

These v intermediates consist of phenazines, and more particularly the substituted phenazines.

In manufacturing sulphur colors from intermediates, like m'ethyl-hydroxy-amino-phenazine or diaminophenazine and substituted diphenyl amines and paramidophenol and their homologs, it has been customary to employ, as thionating agents, alkali metal polysulphides or mixtures of soda ash, sodium sulphide and sulphur. I have discovered that by the use of a hot solution of certain alkylene amines and sulphur containing substances, sulphur colors are produced giving difierent shades and properties as compared with those obtained when using the thionating agents, which are at present being used in the manufacture ofsulphur colors from these same intermediates. As a specific instance, a hot solution of ethylene diamine and sulphur, or homologs of same and sulphur will produce the above stated shades.

In the following examples, it should be understood that I am not restricted as to temperature, duration of time, or quantities used, as various shades of colors result at temperatures ranging from C., or even less, up to 200 C. The reactions given further can be performed successfully under pressure, such as in an autoclave.

It should further be understood that while these examples disclose the use of water or glycerine as the liquid medium for the thionating, other higher boiling point media can be used, such as ethylene glycol, ethyl ether of ethylene glycol, butyl ether of ethylene glycol, and, also, the higher boiling alcohols, such as butyl, amyl, and hexyl alcohols, or a mixture or any two or more thereof.

It should, also, be understood that a wide range of sulphur color intermediates can be thionated by this method.

The alkylene amines which I use are of the higher boiling types, such as ethylene diamine, tetra ethylene triamine, penta ethylene tetramine, propylene diamine, etc., and their homologs.

Example 1.-35 parts, by weight, ethylene diamine are heated at 140 C. with 45 parts sulphur for two hours. 50 parts water are added and then, 10' parts vmethyl-hydroxy-amino phenazine are added. The whole is refiuxedfor twenty-four hours at C., the mixturefis then poured into 1,000 parts water, air is blown in until the dyestuiiis precipitated. The dyestuff is then filtered and dried and is now ready for use, giving a'.red.brown shade. 1

Example 2.35 parts, by weight, ethylene diamine are heated ail-I 0? C. with 4 5 parts su1-. phur for two hours. 50 parts water are added and then 10 parts dinitro-para-hydroxy diphenylamine are added. The whole is refluxed for twenty-four hours at 115 C., the mixture is then poured into 1,000 parts water, air is blown in until all the dyestuff is precipitated. The dyestuii is then filtered and dried and is now ready for use, giving a blue black shade.

Example 3.-35 parts, by weight, ethylene diamine are heated at C. with 45 parts sulphur for two hours. 50 parts glycerine are added and then 10 parts methyl-hydroxy-aminophenazine are added. The whole is refluxed for two hours at C., the mixture is then poured into 1,000 parts water, air is blown in until all the dyestuff is precipitated. The dyestufi is then filtered and dried and is now ready for use, giving a red brown shade.

Example 4.-45 parts, by weight, tetra ethylene triamine are heated at 50 C. with 45 parts sulphur for two hours. 50 parts glycerine are added and then 10 parts paramidophenol base are added. The whole is refluxed for two hours at C., the mixture is then poured into 1,000 parts water, air is blown in until all the dyestuif is precipitated. The dyestufi is then filtered and dried and is now ready for use, giving an olive drab shade.

I claim:

1. In a method of preparing sulphur colors from dyestuff intermediates that are thionated toproduce dyes by means of thionating agents, thionating a dyestufi intermediate selected from a group consisting of amino phenols of the benzene series, amines of the benzene series, and phenazines, in a medium prepared from ethylene diamine and sulphur heated together for substantially two hours at substantially the range 140 to 150 C., in which medium the said intermediate is converted into a sulphur color.

2. In a method of preparing sulphur colors from phenazines that are thionated toproduce dyes by means of thionating agents, thionating a phenazine in a medium prepared from ethylene diamine and sulphur heated together for substantially two hours at substantially 140 to substantially 150 C., in which medium the phenazine is actively converted into a sulphur color.

3. The process of manufacturing sulphur colors, which consists in heating parts, by weight, of ethylene diamine with parts, by weight, of sulphur to a temperature of about 140 C.', for a period of about two hours, adding thereto parts, by weight, of water and then 10 parts, by weight, of methyl-hydroxy-aminophenazine, refluxing the whole for a period of about twenty-four hours, at a temperature of about C., pouring the mixture into 1,000 parts, by weight, of water, then blowing air into the mixture until the dyestuif is precipitated, and then filtering and drying the said dyestufi.

4. The process of manufacturing sulphur colors, which consists in heating 35 parts, by Weight, of ethylene diamine with 45 parts, by weight, of sulphur to a temperature of about C., for a period of about two hours, adding thereto 50 parts, by weight, of water and then 10 parts, by weight, of dinitro-para-hydroxy diphenylamine, refluxing the whole for a period of about twentyfour *hours, at a temperature of about 115 C., then pouring the mixture into 1,000 parts, by weight, of water, then blowing air into the mix? ture until all the dyestuff'is precipitated, and then filtering and drying the said dyestufl.

35. The process of manufacturing sulphur colors, which consists in heating 35 parts, by weight, of ethylene diamine with 45 parts, by Weight, of

sulphur to a temperature of about 140 C., for a period of about two hours, adding thereto 50 parts, by weight, of glycerine and then 10 parts, by weight, of methyl-hydroxy-amino-phenazine, refluxing the who-1e for a period of about two hours, at a temperature of about 170 C., then pouring the mixture into 1,000 parts, by weight, of water, then blowing air into the mixture until all the dyestuff is precipitated, and then filtering and drying the said dyestufi.

6. In a method of preparingrsulphur colors, thionating methyl hydroxy-amino-phenazine in a medium prepared from ethylene diamine and sulphur heated together for substantially two hours at substantially 140 to C., in which medium methyl hydroxy-amino-phenazine is converted into a sulphur color.

'7. In a method of preparing sulphur colors, thionating para-aminophenol in a medium prepared from ethylene diamine and sulphur heated together for substantially two hours at substantially 140 to 150 C., in which medium parae amino-phenol is converted into a sulphur color.

8. In a method of preparing sulphur colors, thionating dinitro-para-hydroxydiphenyl-amine in a medium prepared from ethylene diamine and sulphur heated together forsubstantially two hours at substantially 140 to 150 .C., in which medium dinitro-para-hydroxydiphenyl-amine is converted into a sulphur color.

SIMON NORMAN. 

